Catalytic dehydrogenation process



United States Patent 3,461,183 CATALYTIC DEHYDROGENATION PROCESS Harold J. Hepp and E. 0. Box, .lr., Bartlesville, Okla,

assignors to Phillips Petroleum Company, a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 615,078, Feb. 10, 1967. This application Nov. 8, 1967, Ser. No. 631,562

Int. Cl. C07c /18, 5/30 US. Cl. 260-680 11 Claims ABSTRACT OF THE DISCLOSURE Alkanes, cycloalkanes, arylalkanes, and certain substituted alkanes, and particularly n-butane, diluted with steam, are dehydrogenated (in a single stage or in two stages) in the absence of free 0 at high conversion and selectivity to less saturated compounds with a catalyst composite including one or more metals of the platinum group and nickel deposited on a support such as alumina, silica, or a Group II aluminate spinel which is alkalized with an alkali or alkaline earth metal compound such as K CO or BaO to impart a pH of at least 8 to the composite. Catalysts using platinum group metals are found to have longer life on-stream when prepared from compounds of these metals having no nonvolatile radicals.

This application is a continuation-in-part of application, Ser. No. 615,078, file'd Feb. 10, 1967, now abandoned.

The invention relates to an improved process for the dehydrogenation of dehydrogenatable hydrocarbons and certain substituted hydrocarbons.

It is conventional in the dehydrogenation of paraflin hy drocarbons to utilize catalysts such as nickel-kieselguhr, chromium oxide-alumina, zinc oxide-alumina, platinumalumina, and the like. In general, prior art processes are operated with a water-free feed stock and at a low pressure. Considerable advantages are inherent in any process that can operate with steam. For instance, heat of reaction can readily be supplied. Coke deposition on the catalyst can be retarded. Expensive compression of products can be avoided since elevated pressure can be employed and steam can readily be condensed after dehydrogenation is elTecte-d. For reasons such as these, various attempts have been made to employ steam in processes for the de hydrogenation of paraflin hydrocarbons. One of the most successful catalysts to effect this result is broadly disclosed in US. 3,168,587 wherein a platinum catalyst on a support such as Zinc aluminate is disclosed to be one possible catalyst for the dehydrogenation of paraflin hydrocarbons in the presence of steam and oxygen.

We have now found that highly active catalysts for the dehydrogenation of steam-diluted alkanes, cycloalkanes, arylalkanes, and substituted alkanes in which a stable nitrogen-containing heterocyclic radical has been substituted for a hydrogen, can be prepared by treating certain Group VIII metal catalysts that are supported on spinel compounds, such as zinc aluminate spinel, with sufiicient Group Ia and/or Group IIa compounds (such as the carbonates, acetates, hydroxides, and the like of sodium, calcium, magnesium, beryllium, barium, and the like), to neutralize the acid sites of the supported catalyst (efiecting a pH of at least 8) and thus promote the activity of the supported platinum and/or other Group VIII metal catalyst for effecting the dehydrogenation of alkanes, etc., in the presence of substantial volumes of steam. Other porous carriers enumerated below may be substituted for the spinel compound but their use results in the formation of somewhat less active catalysts.

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The Periodic Table referred to herein is that published in the Chemical Rubber Companys Handbook of Chemistry and Physics, 45th edition (1964), page 13-2.

The catalysts of our invention can be prepared by combining, in any manner known to the art, certain Group VIII metal or metal compounds capable of reduction including nickel, platinum, ruthenium, palladium, iridium, rhodium, osmium, and mixtures thereof, with a base or support selected from the members alumina, HF-treated alumina, silica, magnesia, zirconia, aluminosilicates, Group II aluminate spinels, and mixtures thereof, including mixtures of spinel and excess Group II metal oxide or spinel and excess alumina, and further treating the resulting composite by any means known to the art with at least one alkali or alkaline earth metal compound, such as sodium hydroxide, potassium carbonate, lithium hydroxide, barium acetate, barium hydroxide, calcium oxide, and the like, so as to impart to the resulting composite an alkaline pH of at least 8. The Group VIII metal content of the' catalyst should be in the range of 0.1 to 5 weight percent of the support 'or base. Throughout this application the term weight percent of the support or base means parts by weight per parts by weight of support or base. Sufiicient alkali or alkaline earth metal compound or compounds are used to neutralize the acid sites of the catalyst composite including the metal and support, to leave the composite alkaline, and to activate the catalyst for the dehydrogenation of steam-diluted alkanes. The optimum amount of each alkali or alkaline earth metal compound or combination of compounds for each supported metal catalyst must be determined experimentally, but usually an amount in the range of 0.5 to 10 weight percent of the total catalyst is effective. However, sufiicient alkaline material must be employed to impart an alkaline pH of at least 8 to the catalyst.

We have also found that preparing the catalyst of the invention with platinum group metal compounds containing no nonvolatile acidic radicals imparts long onstream life to the catalyst. Preferred compounds of this type are the complex or coordination compounds of the platinum metals.

Any platinum-group metal compound containing no nonvolatile acidic radical can be used. In the discussion of the compounds that can be used the platinum compounds will be used as nonlimiting examples. It is to be understood that similar compounds of the other platinum-group metals can be used. Examples of simple or non-coordination compounds that can be use-d are platinic chloride, chloroplatinic acid, ammonium chloroplatinate, and the like. Many complex or coordination divalent and tetravalent platinum compounds are known in which there are four and six groups, respectively, inside the complex, and either none, one, or two, or none, one, two or four radicals, respectively, outside the complex. The groups inside the complex can be neutral, e.g., hydrocarbyl, amine, hydroxylamine, ethylenediamine, hydrazine, CO and the like; basic, e.g., hydroxy, and the like; or volatile acidic, e.g., nitrite, nitrate, CN, carbonate, and the like. When added to the support from solution, some of the compounds can be added from aqueous solution, but others will require nonaqueous solvents such as alcohols, hydrocarbons, ethers, ketones, and the like. Nonlimiting examples of coordination platinum compounds that can be used are: platinum amminoacetate, platinum dimethyl dioxime, platinum diammine dinitrate, platinum tetraammine dihydroxide, platinum diammine dihydroxide, platinum hexammine dihydroxide, platinum hexammine tetrahydroxide, platinum diammine tetrahydroxide, platinum diammine dihydroxide dinitrate, platinum diammine tetranitrate, platinum diammine dinitrite, platinum tetraarnmine dicarbonate, platinum diammine oxalate, and the like.

The catalyst systems of this invention are employed at temperatures between 750 and 1250 F., preferably between 1000 to 1100 F., and at pressures in the range of to 500 p.s.i.g., preferably 0 to 250 p.s.i.g. Steam to hydrocarbon mol ratios of 0.5:1 to 30:1, preferably 2.5:1 to :1, are employed. Total space velocity (GHSV) of hydrocarbon and steam is between 100 and 50,000, preferably between 500 and 20,000 volumes of gas/volume of catalyst/hour (32 F., p.s.i.a. absolute pressure).

The modified catalysts of the invention are particularly well adapted to the dehydrogenation of alkanes, cycloalkanes, and arylalkanes containing from 2 to 12 carbon atoms. These hydrocarbons include ethane, propane, butanes, octanes, dodecanes, cyclohexane, cyclododecane, cyclopentane, ethyl benzene, n-butylbenzene, and the like. In addition, compounds that optionally contain a stable heterocyclic moiety such as pyridyl, piperidyl, and the like, substituted for a hydrogen of such hydrocarbons are effectively dehydrogenated with the modified catalyst in the presence of steam and in the absence of oxygen. Examples of such substituted compounds include 3-ethylpyridine, 4-propylpyridine, 3-n-butylpiperidine, and the like. Catalysts prepared by depositing the selected dehydrogenating metal on spinels and alkalizing the composite are preferred to those utilizing other supports or bases because of their higher conversion activity and selectivity for olefins. Spinels, as referred to herein, are compounds of the formula M (AlO or MO-Al O wherein M is a group Hz: or IIb metal ion with a valence of 2.

In one embodiment of the invention, C to C parafiln hydrocarbons such as n-butane, n-pentane, isopentane and the like, are dehydrogenated to the corresponding diolefins, i.e., 1,3-butadiene, 1,3-pentadiene, isoprene, and the like, the dehydrogenation being effected in first and second dehydrogenation zones in series. In this operation, steam and the steam-active catalysts of the invention are used in the first zone. The effluent from the first zone, including steam, hydrogen, olefin, diolefin, and unreacted parafiin, is passed to the second zone where it is contacted with a steam-active olefin dehydrogenation catalyst.

Olefins, diolefins, unreacted paraffin, water (steam), and hydrogen are separately recovered from the efiluent from the second zone. Recovered olefin is recycled to the second zone and recovered paraffin is recycled to the first zone. Steam is generally added to the efiluent from the first zone (feed to second zone) for temperature control.

Operating conditions for the first dehydrogenation zone are those disclosed herein for dehydrogenating with our improved catalyst. The dehydrogenating conditions used in the second zone to effect olefin dehydrogenation are those found in US. patent to E. W. Pitzer 2,866,790 and include a temperature in the range of about l0501300 F., steam to olefin mole ratio of about 1:1 to :1, olefin space velocity in the range of 100 to 1000 v./v. cat./hr., and a pressure of atmospheric or higher.

The olefin dehydrogenation catalyst is an alkalized iron oxide containing one or more promoters and/or stabilizers such as Cr O These catalysts are more fully disclosed in US. patents Pitzer 2,866,790; Kearby 2,426,829; Gutzeit 2,408,140; and Eggertsen et al. 2,414,585. A representative catalyst comprises by Weight about 45 percent Fe O 5 2 percent K CO 3 percent Cr O EXAMPLE I A catalyst support wherein the atom ratio of Zn to Al was 1:1 was prepared by coprecipitating a zinc oxidealuminum oxide gel from a solution of zinc nitrate and aluminum nitrate with ammonium hydroxide, allowing to stand for 1 hour, filtering, washing repeatedly, drying under heat lamps, sieving to 8-20 mesh (U.S. Sieve), and heating to 850 F. in air for several hours. The calcined spinel thus formed had a pH of 6.7 in water (2 g. sample of catalyst in 50 cc. of water); it was actually a mixture of the spinel ZnO-Al O and ZnO. This calcined spinel support was then charged to a reactor and a stream of n-butane and stream was charged to the reactor as presented below in run 1. Samples were taken one hour after the initial steady state conditions were established. After run 1 was completed, the zinc spinel was heated in the presence of oxygen to remove any carbon and removed from the reactor. In this and other carbon-removal operations described in the examples carbon removal was effected during a 1-hour period using air or nitrogen-diluted air at such dilution and flow that the maximum temperature in the catalyst bed did not exceed 1050 F. It was then soaked in aqueous platinic chloride solution in such manner as to impregnate with 0.56 wt. percent Pt based on the zinc spinel. The Pt-zinc spinel catalyst was charged to the reactor and n-butane and steam were charged for run 2 as presented below. In like manner, after run 2, the catalyst of that run was heated in the presence of oxygen to remove any carbon deposits, removed, soaked in aqueous K CO solution in such manner as to impregnate with 2.0 wt. percent K CO based on the zinc spinel, and charged to the reactor. Run 3 was made in like manner as is presented below. Before each run the catalyst was reduced in H at 1000 F. Such treatment with hydrogen is not essential, but is desirable for the first run made with a freshly prepared catalyst of this type to stabilize activity more rapidly.

Run 1 Run 2 Run 3 Catalyst Zinc spinel Zinc spinel Catalyst of plus 0.56% Run 2 plus P13 2.0% KzC O 3 Temp.,F 1,105 1, 045 1, 032

Pressure, p.s.i.g 115 115 Moles steam/moles C H 3. 9 4. 0 4. 3

Catalyst pH 6. 7 7 10. 4

SV, total. 2, 400 2, 400 2, 400

Conversion, percent 9. 2 37. 7 31. 8 Distribution of reaction products, mole percent:

Methane+etl1ene 69 10. 2 4. 7

nil 55. 2 80.8

nil nil 2. 0

This example clearly demonstrates that the combinatron of components of the catalyst system of this inventron are necessary to provide a superior catalyst system.

EXAMPLE II A zinc oxide-aluminum oxide gel (ZnO/A1 O ratio of 1/1) was prepared by the addition of 216 ml. of 28% ammonium hydroxide in 1000 ml. water to 5000 ml. of aqueous solution containing 119 gm. of zinc nitrate (hydrated) and 300 gm. of aluminum nitrate (hydrated) with vigorous stirring. The gel was allowed to stand 1 hour and was then filtered in Biichner funnels. The filter cake was washed repeatedly to remove the ammonium nitrate and then was dried under heat lamps. After drying and sieving to 820 mesh, the zinc aluminate was heated to 1000 F. in air for several hours. The calcined spinel was then soaked in aqueous PtCl such that 0.5 wt. percent platinum based on spinel was absorbed. The catalyst was again dried under heat lamp. It was then impregnated with aqueous potassium carbonate of such strength that after final drying the catalyst contained 2.0 wt. percent of potassium carbonate. This catalyst was reduced in H flow at 1000 F. for about 1 hour immediately prior to a test of activity.

A mixture of steam and normal butane (3.6/1 steam/ butane mole ratio) was fed over the catalyst described above at 75 p.s.i.g. total pressure, 1045 F., and 2120 total gas hourly space velocity. After nine hours without regeneration, the butane conversion was still 30.5% with a selectivity of 78.4 mole percent to butenes and butadiene. A sample of the dry gas effluent at this time had the following composition:

Mole percent Only 5.4% of the reacted butane went to carbon oxides with 16.4% to C -C components.

Following the procedure a-bove, another portion of zinc aluminate spinel was impregnated with 0.6 wt. percent platinum. After drying, it was then impregnated to contain 6.4% calcium acetate (monohydrate). The final step before calcination was to impregnate to add 0.5 wt. percent potassium carbonate. This catalyst was calcined at 1000 F., then reduced in hydrogen at 1000 F. for about 1 hour.

In a test at 980 F., 100 p.s.i.g., 4180 total gas hourly space velocity, and 6.06 moles of steam per mole of normal butane, the conversion of butane was 27.9% after 6.7 hours. At this time 84.7 mol percent of the reacted butane was converted to butenes and butadiene. Only 8.2% of the reacted butane was converted to C -C cracked products and 6.2% to CO and C0 The eflluent dry gas had the following composition:

This example demonstrates that various alkali or alkaline earth compounds and combinations thereof can be employed as the third component of the catalyst system.

EXAMPLE III Following the same procedure for preparing a spinel as described in Example II, one was prepared where 50% of the zinc was replaced by barium. The calcined spinel was then a 50-50 coprecipitated mixture of Zinc aluminate and barium aluminate. The calcined spinel was impregnated with aqueous PtCl to add 0.5 wt. percent platinum and tested for dehydrogenation activity.

After the test the catalyst was removed from the reactor and impregnated with aqueous calcium acetate to contain 2 wt. percent calcium oxide after calcination. A test was again made under like conditions and the advantage of the addition of the alkaline earth oxide may be observed by a comparison of the data from the two tests:

50-50 BaAlzot and ZnAlzO; Same with with 0.5% 2.0% CaO Pt added Temp, F 1, 020 1, 016 Pressure, p.s 1 g. 75 75 Steam/C4, mole ratio 3. 6 3. 8 GHSV, total 2, 135 2, Butane conversion, percent 35. 8 36. 3 D1str1bnti0n of reacted butane, mole iii C C d rac mg 3001111301111 s 31.9 19. 7 +00: 9. 0 7. 5 Butenes-i-butadiene selectivity 59. 1 72. 7 Dry efiiuent analysis, mole percent:

H1 35. 1 34. 6 2. 7 2. 7 0. 4 0. 2 6.7 5. 9 0. 9 1. 3 5. 6 2. 9 1. 3 0. 7 35. 6 36. 9 11. 4 14. 5 Butadiene 0. 3 0. 3

This example demonstrates the latitude that can be practiced in formulating the catalyst system of this invention in that spinels other than zinc aluminate can be employed.

'EXAMPLE IV Run 1 Run 2 Run 3 Run 4 Temperature, F 1,025 1, 037 1, 041 1, 043 Time, hours 0. 25 1. 0 2. 0 3. 0 Conversion, percent 38. 8 25. 9 20. 1 15. 8

Distribution of products, mole percent:

58. 7 44. 4 40. 3 34. 5 23. 7 27. 4 28. 3 29. 3 17. 6 28. 2 31. 4 36. 2 nil nil nil nil EXAMPLE V A catalyst consisting of 0.5 wt. percent platinum and 8.8 wt. percent barium oxide on a zinc aluminate spinel support was prepared by the method of Example II. Results obtained in butane dehydrogenation after about 14 hours without regeneration and after regeneration are presented below:

Run 1 Run 2 Run 3 Run 4 Regenerated" Temperature, F 1,037 1,047 1,033 1,033

none 2. 7 6. 7 none Pressure, p.s.1.g 7.5 75 75 75 Conversion, percent. 29. 3 9. 0 37. 5 37. 6 Distribution of Products,

mole percent:

CO+CO2 3.7 4.8 7.7 5.0

Butadiene 3. 2 2. 6 2. 2 2. 3

*Catalyst was heated in the presence of oxygen to remove any carbon deposits at 16.5 hours.

These data clearly show that the addition of air to the feed stream as is called for in US. 3,168,587 is deleterious to the process of this invention in that conversion and selectivity to butenes are both adversely affected, and an undesirable degree of water-gas activity and undesirable cracking are promoted. This example also further demonstrates the stability of the catalyst of this invention over long runs without the necessity of regeneration. Also demonstrated in the fact that barium oxide is quite suitable as a component of the catalyst system of this invention.

EXAMPLE VI Three catalysts were used to further demonstrate the process of the invention:

Catalyst A: This catalyst was prepared by impregnating a portion of Universal Oil Products Company Penex catalyst with suffieient aqueous potassium carbonate solution to give 2 weight percent K CO drying, and calcining at 1000 F. in hydrogen before use. The Penex catalyst contains about 0.36 weight percent platinum and 3.4 percent fluorine, the balance being active alumina, and is believed to have been prepared by the process of US. 2,689,226. It is in the form of about 1.5-mm. diameter spheres. The pH of the calcined catalyst was 9.5.

Catalyst B: A -20 mesh gamma alumina having a surface area of 360 square meters per gram was impregnated with an aqueous platinic chloride solution to give 0.5 weight percent platinum, dried, impregnated with an aqueous potassium carbonate solution to give 2.5 weight percent K CO dried, and calcined at 1000 F. in hy- 8 EXAMPLE v11 A Zinc aluminate spinel prepared in the manner described in Example II was impregnated with an aqueous solution of platinum tetraammine dihydroxide to give 0.5 weight percent platinum, the resulting composite being dried under a heat lamp until free flowing after which it was impregnated with an aqueous solution of lithium nitrate to give 0.5 weight percent lithium. The resulting composite was dried under a heat lamp until free flowing after which it was placed in the reactor, heated to reaction temperature in air and calcined in air at that temperature for about 2 hours, reduced .in hydrogen, tested in butane dehydrogenation. It should be pointed out that the hydrogen reduction step is not an essential step. The catalyst was regenerated four times. Regeneration was effected by stopping hydrocarbon and steam flow, flushing with nitrogen, and passing a nitrogen-air mixture containing about 10 volume percent oxygen over the catalyst at 900 F. and a space velocity of about 3000 volumes per volume of catalyst per hour for a period of to 60 minutes. Oxygen content of the regeneration gas and reactor temperature are controlled such that the catalyst temperature does not exceed about 1050 F. The data obtained in the runs are presented below:

Temp, F 1, 044 1, 050 1, 044 1, 047 1, 048 1, 048 1, 047 1, 048 1, 046 Pressure, p.s.I.g. 80 80 80 80 85 80 80 80 80 Steam/n-Ca, mol ra 4. 7 4. 1 4. 2 4. 2 4.2 4. 2 4. 2 4. 2 4. 2 GHSV (Total), v./v./hr. (14

32 F 6, 820 6, 870 6, 850 6, 880 6, 820 6, 880 6, 880 0, 860 6, 880 Total time on stream, hours... 2. 0 28. 29. 5 51. 0 53. 79. 0 80. 84. 5 85. 5 Regenerated catalyst, hours 28. 51.0 79.0 85. 0 COHV01'S 10I1, percent 36. 6 29. 0 36. 1 29. 6 35. 6 29. 8 33. 9 28. 9 35.6 Selectivity, Incl percent:

Cracking 8. 4 5. 9 8. 0 6. 0 6. 7 5. 7 I. 0 6. 2 7. 6 Water Gas 7. 4 6. 9 7. l 6. 6 6.6 6. 3 6. 7 6. 6 6. 6 Butene-l-butadiene 84. 2 87. 2 84. 9 87. 4 86. 7 88. 0 86. 3 87. 2 85. 8

drogen before use. The pH of the calcined catalyst was 10.4. 1

Catalyst C: A 1020 mesh silica gel was impregnated with an aqueous palladous chloride solution to give 0.46 weight percent palladium, dried, and calcined at 1000" F. in hydrogen before use. This is a catalyst of US. 3,168,- 587. The pH of the calcined catalyst was 6.3.

These catalysts were used to dehydrogenate propane or butane:

A B B C Propane Butane Butane Butane Steam/bye, mol. 3. 9 3. 8 3. 8 3. 5

1 This is equivalent to 2.7 mol percent oxygen, based on the butane. 2 01-02 in Run 1; 01-0 in Runs 2-4.

3 Propylene in Run 1; butenes in Runs 2-4.

4 Including 0.2 mol percent butadiene.

These data show that good olefin yields are obtained with catalysts of the invention (Catalysts A and B) in the absence of oxygen (Runs 1 and 2), that addition of oxygen to a catalyst of the invention (Catalyst B) results in a marked decrease in olefin yield, and that a catalyst of US. 3,168,587 (Catalyst C) is relatively inactive under the conditions of our inventi0ni.e., with steam and without oxygen.

The above data indicate that the catalyst of the invention, prepared using platinum metal compounds free of nonvolatile acid radicals, can be used for 25 to 30 hours between regenerations, with only a small decrease in n-butane conversion. In similar runs with a catalyst prepared with platinum compounds containing a nonvolatile acid radical but otherwise prepared in the same manner, n-butane conversion decreased to less than 20% in runs of the same length.

Certain modifications of the invention will become apparent to those skilled in the art and the illustrative details disclosed are not to be construed as imposing unnecessarv limitations on the invention.

We claim: 1. A process for dehydrogenating a dehydrogenatable hydrocarbon of from 2 to 18 carbon atoms of the group alkanes, cycloalkanes, and arylalkanes, which comprises contacting at least one compound of said group in admixture with steam in a mole ratio of steam to dehydrogenatable compound in the range of 0.5:1 to 30:1 and in the absence of free 0 under dehydrogenating conditions with a catalyst composite including the components (a) a support of the group alumina, HF-treated alumina, silica, magnesia, zirconia, alumino-silicates, Group II aluminate spinels, and mixtures thereof,

(b) a metal obtained from the decomposition by calcination on said support of a metal compound of said metal, said metal selected from the group nickel, platinum, palladium, ruthenium, iridium, rhodium, osmium, and mixtures thereof in an amount from about 0.05 to about 5.0 weight percent of said support, and

(c) at least one compound of a metal of Group Ia or Group IIa in an amount in the range of about 0.1 to about 10 weight percent of said composite sufficient to at least neutralize the acid sites of the supported 9 catalyst and impart to said composite a pH of at least 8.

2. The process of claim 1 wherein component (a) is a calcined Group II aluminate support, said support comprising substantially spinel and at least 5 mol percent metal oxide.

3. The process of claim 1 wherein component (a) comprises essentially a calcined zinc aluminate support, said support comprising substantially spinel and at least 5 mol percent metal oxide.

4. The process of claim 3 wherein component (a) is a calcined zinc and barium aluminate support, said support comprising substantially spinel and at least 5 mol percent metal oxide, and component (b) comprises essentially a platinum group metal.

5. The process of claim 1 wherein component (a) comprises essentially said calcined support, said support comprising substantially spinel and at least 5 mol percent metal oxide, component (b) comprises essentially at least one platinum group metal resulting from the decomposition of a platinum group metal compound free of nonvolatile acid radicals, and said dehydrogenatable compound comprises essentially a dehydrogenatable hydrocarbon of form 2 to 20 carbon atoms of the group a1- kanes, cycloalkanes, and arylalkanes.

6. The process of claim 5 wherein said alkane is nbutane.

7. The process of claim 1 wherein component (a) is active alumina, component (b) comprises essentially platinum, and said dehydrogenatable compound comprises essentially n-butane.

8. The process of claim 1 wherein said dehydrogenatable compound is a C -C parafiin hydrocarbon dehydrogenatable to a diolefin, said dehydrogenation is effected in two stages, in a first dehydrogenation zone under the conditions of claim 1, substantially the entire efiiuent from said first zone being passed to said second zone as feed in contact therein with steam active olefin dehydrogenation catalyst, paraffin hydrocarbon being recovered from the second zone efliuent and recycled to said first zone, and olefins being recovered from said second zone effiuent and recycled to said second zone.

9. The process of claim 8 wherein said parafiin hydrocarbon is n-butane.

10. The process of claim 8 wherein said parafiin hydrocarbon is n-butane, component (a) of said catalyst is a Group II aluminate calcined support, said support comprising substantially spinel and at least 5 mol percent metal oxide, and component (b) is platinum obtained from a platinum compound of a volatile radical and platinum.

11. The process of claim 1 wherein the said metal of component (b) is selected from the group platinum, palladium, ruthenium, iridium, rhodium, osmium, and mixtures thereof.

References Cited UNITED STATES PATENTS 3,126,426 3/1964 Turnquest et a1. 260-6833 3,168,587 2/1965 Michaels et a1. 260-6833 3,293,319 12/1966 Haensel et al. 260-6833 3,315,008 4/1967 Abell et a1 260-6833 3,360,586 12/1967 Bloch et al. 260-6833 3,373,219 3/1968 Kroenig et a1 260-6815 3,363,023 1/1968 Mooi et a1 260-683.3

DELBERT E. GANTZ, Primary Examiner G. E. SCHMITKONS, Assistant Examiner US. Cl. X.R. 260-683 

